Cyanoethylated anilides and phenylene bis acid amides



United States Patent CYANOETHYLATED ANILIDES AND PHENYLENE BIS ACID AMIDES Saul R. Buc, Easton, Pa., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application April 10, 1956, Serial No. 577,198

12 Claims. (Cl. 260-465) and =1 C H2 0 H] C N wherein R represents either hydrogen or lower alkyl, e. g., methyl, ethyl, propyl or butyl groups, R1 represents 2,809,984 Patented Oct. 15, 1957 ICC 3-nitro butyranilide 3-arnino butyranilide 4-amino butyranilide V 5 i 7 As examples of phenylene bis acid amides which are reacted with 2 moles of acrylonitrile, the following may be employed:

mor p-Phenylene bis-formamide mor p-Phenylene bis-acetamide mor p-Phenylene bis-propionamide mor p-Phenylene bis-butyramide The cyanoethylation of the subject group of compounds is unpredictable and surprising, since we were unable to cyanoethylate p-nitroacetanilide although one could cyanoethylate the meta-nitro, isomer.

Further details regarding the process will become clearly manifest from the following working examples:

Example I omomcN I III-C0011:

p In a flask equipped with a reflux condenser 9,0 grams of 3-nitro acetanilide, 5.0 ml. of. .trimethyl' be'nzylammonium hydroxide and 150 ml. of acrylonitrile'were mixed, and the mixturerefluxed'for a period of 16 hours. Thereafter, the excessacrylonitrile was distilled, the remaining residue was poilredinto water where it slowly crystallized. The crystals were filtered, washed with water and dried, yielding 106 grams, or 91% of theory of a product having a melting point of 75-79 C. A sample of crystallized petroleum ether melted at 81-82.5 C.

either hydrogen, amino. ornitro group, R2 represents either hydrogen or amino, and wherein one but not both R1 and R2 groups represent hydrogen.

The compounds characterized by the foregoing general formulae are readily prepared by reacting 1 mole of an amino or nitro substituted anilide with 1 mole of acrylonitrile or by reacting 1 mole of either mor p-phenylene bis acid amide with 2 moles of acrylonitrile in the presence of an inert solvent-diluent such as dioxane and in the presence of an alkaline condensing agent such as trimethyl benzyl ammonium hydroxide. The amount of the latter may range from 5 to 50 parts per 100 parts of acrylonitrile. The amount of dioxane is immaterial so long as a sufiicient amount is employed to permit stirring of the reaction mixture.

As examples of anilides which are condensed with 1 mole of acrylonitrile, the following are illustrative:

S-nitro formanilide 3-amino formanilide 4-amino formanilide 3-nitroacetanilide 3-aminoacetanilide 4-aminoacetanilide 3-nitro propionanilide 3-amino propionanili'de 4-amino propionanilide The product may be reduced to form the product of Example II. p

An attempt to cyanoethylate 4-nitro acetanilide under identical conditions was unsuccessful. The starting materials were recovered unchangedl'l Example 11 CHzCHeCN N- oocni In a flask equipped with a stirrer there were charged I grams of 3-amino acetanilide,v 100 ml. of dioxane, and 1.5 ml. of trimethyl benzyl ammonium hydroxide. To

me charged mixture was added dropwise with stirrer 100 ml. of acrylonitrile. The temperature rose spontaneously to 35 C. for 2 /2 hours and then allowed to drop. The

mixture was allowed to stand over night and the acrylonitrile and dioxane distilled in vacuum. The residue weighed 76 grams or 81.2% of theory, and is an oil which crystallized on long standing to an oily crystalline mass.

Attempts to carry out the reaction without dioxaneled to an uncontrollably violent reaction. p

Example III CHzCHzCN N-C OOH:

2,809,984 v i s r 4 In a flask equipped with a reflux condenser there were dihydroxy anthraquinone with an aryl amine such as charged 150 grams of 4-amino acetanilide, 200 ml. of p-aminoacetanilide. acrylonitrile, and 5 ml. of trimethyl benzyl ammonium hydroxide. There was no spontaneous heat evolution, and accordingly, the mixture was refluxed for a period of 24 hours. Theexcess' acrylonitrile was removed by distillation in vacuum. The residue weighed 268 grams. I I ,1 The theoretical yield is 203 grams. The excess weight is most likely polymerized acrylonitrile. The product was separated from the polymer by soluti-on in a slight ex- N OHO cess of cold dilute hydrochloric acid, decanting from the tarry polymer and charcoaling and filtering the aqueous GHzCHgCN solution and the product precipitated as an oil by the addition of an aqueous solution of potassium carbonate. 2 a flask i fi 1 i g y; i g i It was then extracted from the water with chloroform grams 0 any ene 18' Ormaml o Exaniple VII CHzCHzCN and dried over potassium carbonate and the chloroform dioxane and 5 of mmethyl ibenzyl ammonium hydroxdistilled. The weight of the final oily product was 194 To the charge? imxture there was added dropwtlfie grams which couldnot be made to crystallize. 'acrylommle' temperature rose as e amide dissolved as the reaction proceeded. The tem- Example IV 20 perature was not allowed to exceed 50 C. After the end of the addition of the acrylonitrile, the reaction mixture was allowed to stand over night. The homogeneous PPCOCEHCH: mixture on scratching and cooling gave an essential quantitative yield of crystallized product. It was filtered, washed with cold dioxane and dried. It has a melting point of 114-117 C.

N a When insuflicient acrylonitrile is used, a mixture of Example I was repeated with the exception that '90 I grams of 3-nitroacetanilide were replaced by an equivalent N-CHO amount of 3-nitro propionanilide.

The product may be reduced as in Example I to form the corresponding amino derivative.

NHCHO Example V 85 CH2CH CN and N-CHO CH2CH2CN N-CHO j N-CHO Example H. was repeated with the exception that 60 CHZCHzCN grams of 3-am1n0acetan1l1de were replaced by an equivalent amount of 4-amino formanilide. is obtained admixed with unreacted starting product,

Example VI m-phenylene bis-formamide.

CHZCHICN Example VIII N-COCHzCHzCH: OCHN-CHaC 2CN I r NH: OCHNCH:CH2CN Example III was repeated with the exception that 150 grams of 4-aminoacetanilide were replaced by an equivalent amount of 4-amino butyranilide.

The nitro group of the products of Examples I and IV is readily converted by conventional means to an amino group. The resulting amino containing compound and Example VII was repeated with the exception that 164 grams of m-phenylene bis-formamide was replaced by the same amount of p-phenylene bis-formamide, and the volume of dioxane increased by 100 ml. The yield of the final product was 243 grams which is equivalent to 87% I of theory.

those of Examples II, III, V and VI are useful as mter- Example 1 mediates in the preparation of anthraquinone dyes possessing excellent gas and light fastness when dyed on CHQCHYCN, cellulose ester fibers. For example, they may be con- N-COCHzCH:

densed with 4,5-dinitro chrysazine or 4,8-dinitroanthrarufin to yield dyestuffs which dye acetate rayon blue shades possessing outstanding light and gas fastness. It 4 is the presence of the mor p-amino cyanoethylated N-COCHzCHl anilide group in the nitro anthraquinone dye which im- VCH2CH2CN parts constant blue shades of superior fastness. Moreover, such dyestuffs possess three to four times as much EXample VII Was repeated'wlih the eXCePtIOIl that 164 affinity, i. e. substantivity to cellulose acetate than any gr of m-p ny 'bis-formamide Were replaced y of the dyes prepared by heating a mixture of leuco-1,4,5- an equivalent amount of m-phenylene bis-propionamide.

Example X N-COCH:CH2CH:

CHaCHzCN Example V'II was again repeated with the exception that the 164 grams of p-phenylene bis-formamide were replaced by an equivalent amount of p-phenylene bisbutyramide.

The products of Examples VII to X inclusive are useful in solubili zing alkali metal salts of sulfuric acid esters of leuco vat dyes in aqueous printing paste formulations. This solubilizing property is extremely valuable since one of the major problems in the dye industry is the production of uniform, level, non-sticky dye product. To'efiectuate these desirable properties, it is necessary to have the dyestufl in as fine a state of subdivision as possible, and preferably in solution.

The products of Examples VII to X inclusive enhance the solubility of the alkali metal salts of sulfuric acid ester of leuco vat dyes in aqueous medium thereby leading to level, nuon-sticking dyeings. In addition they have the property in common of enhancing solubilization of dissociable ionic compounds in polar solvents.

The free amino products of Examples II, III, V and VI may be used in the preparation of methine dyes, diazos, azo dyes, and the like.

I claim:

1. A cyanoethylated compound selected from the class consisting of those corresponding to the following formulae:

and

CHzCHgGN u IrF-C-R CHzCHgCN wherein R represents a member selected from the class consisting of hydrogen and lower alkyl, R1 represents a member selected from the class consisting of hydrogen, amino and nitro, R2 represents a member selected from the class consisting of hydrogen and amino, and wherein only one of the R1 and R2 groups represents hydrogen. 2. A cyanoethylated compound having the formula:

GHzCHzCN N-O O C H:

A cyanoethylated compound having the formula:

CHzCHgGN --COCH:

4. A cyanoethylated compound having the formula:

5. A cyanoethylated compound having the formula:

I l-C O CHzOHa 6. A cyanoethylated compound having the formula:

oHroHzoN III-CHO 7. The process of preparing cyanoethylated compounds selected from the class consisting of those corresponding to the following formulae:

CHiOHzCN and CHzCHaCN O N-LR which comprises reacting in the case of compounds A e m le Qjr er leni ril w th o e 1 9i an anilid having the following formula:

wherein R has the same value as above, in the presence of an inert solvent diluent and in the presence of trimethyl benzyl ammonium hydroxide.

8. The process according to claim 7 wherein the anilide is S-nitro acetanilide.

9. The process according to claim 7' wherein the anilide is 3-amino acetanilide.

1 0. The process according to claim 7 wherein the anilide is 4-amino acetanilide.

11. The process according to claim 7 wherein the anilide is 3-nitro propionanilide.

12. The process according to claim 7 wherein the anilide is 4-amino formanilide.

References Cited in the file of this patent UNITED STATES PATENTS 2,538,024 McKinney et al. Jan. 16, 1951 2,722,536, Hoefle et a1 Nov. 1, 19.55

FOREIGN PATENTS 9 7 6,959 France Nov. 8, 1950 

1. A CYANOETHYLATED COMPOUND SELECTED FROM THE CLASS CONSISTING OF THOSE CORRESPONDING TO THE FOLLOWING FORMULAE: 